Aminopolyphosphonic acids and polyphosphonic acids and derivatives for the protection of hair



United States Patent Int. Cl. A61k 7/12 US. Cl. 42 4-62 6 Claims ABSTRACT OF THE DISCLOSURE In the process of treating hair in very hard water with an oxidizing agent, the improvement which comprises utilizing from 0.01 to 10% by weight of an aminopolyphosphonic acid or derivative thereof or a combination of said aminopolyphosphonic acid and a polyphosphonic acid.

An agent has been described by us in US. Pat. 3,- 202,579, issued Aug 25, 1965, which prevents or minimizes damage to human hair upon bleaching and/or dyeing with substances which release active oxygen. This composition contains as active ingredient substances selected from the group consisting of at least one oxidizing dye, a bleach, and mixtures thereof, plus 0.01 to 10 percent of a substance selected from the group consisting of phosphonic acid derivatives (acylation products of phosphorous acid) their water-soluble methanol, ethanol, propanol, butanol, and amyl alcohol esters, and their sodium, potassium, ammonium, and ethanolamine salts; said phosphonic acid derivatives having the formula wherein R and R individually are selected from the group consisting of hydrogen and an alkyl having 1 to 5 carbon atoms; X is selected from the group consisting of OH and NH and R is selected from the group consisting of phenyl, a saturated aliphatic group having 1 to 5 carbon atoms, and the group having the configuramen The object of the invention is an improvement of the agents which prevent damage to human hair upon bleaching and/or dyeing. In the past, difiiculties had been encountered when very hard water had been used. When the agents are dissolved in hard water, the solutions are cloudy and the sheen of the hair treated therewith is unsatisfactory.

It now has been found that these drawbacks can be eliminated in such a manner that the phosphonic acid derivatives (acylation products of phosphorous acid) having the Formula 1 wherein R and R individually are selected from the group consisting of hydrogen and an alkyl having 1 to 5 carbon atoms; X is selected from the group consisting of OH and NH and R is selected from the group consisting of phenyl, a saturated aliphatic group having 1 to 5 carbon atoms, and the group having the Formula 2; or the water-soluble esters and the water- 3,542,918 Patented Nov. 24, 1970 soluble salts of the compounds named; are replaced entirely or in part by aminopolyphosphonic acid of Formula 3:

wherein X and Y individually are hydrogen or an alkyl having 1 to 4 carbon atoms; and R and R are either a -PO H group or a group of the Formula 4:

for instance aminotri-(methylenephosphonic acid), ethylenediaminotetra-(methylenephosphonic acid), and diethylenetriaminopenta-(methylenephosphonic acid).

Very good results are obtained with the readily available aminotri-(methylenephosphonic acid).

In lieu of the acids themselves, it frequently has been found opportune in practice to employ the corresponding alkali salts, e.g., the sodium-, potassiumand ammonium salts or also the salts of mono-, diand triethanolamine. All these can be produced by neutralization of the acids. Furthermore, the water-soluble esters are very useful, which are obtained by partial esterification of the acid groups. Appropriate esters are semiesters of the acids with methanol, ethanol, propanol, butanol or amyl alcohol.

The aminopolyphosphonic acids named above can be used singly or in mixtures with each other.

The organic acylation products of phosphorus acid having at least 2 phosphorus atoms in their molecules can be replaced entirely or in part by the aminopolyphosphonic acids named. It also is feasible to employ mixtures of several aminopolyphosphonic acids having at least 2 phosphorus atoms in their molecules.

Especially suitable are those mixtures in which the ratio of aminopolyphosphonic acid to organic acylation products ranges between 3:1 and 1:3.

The materials according to the invention can be admixed to a carrier substance or to a solution, a gel, a cream, paste or powder. They also can be employed in combination with an oxidizing substance. Furthermore, they can be added to such treating agents as rinses or washing agents. The compounds according to the invention are applied in a concentration of 0.1 to 10 weight percent, calculated on the total mixture present, and

preferably in a concentration of 0.1 to 2 weight percent. Larger quantities can be used, however, it has been found that no practical advantages are gained thereby.

The compounds according to the invention have been found to be particularly valuable when extremely hard water is employed. Hair, including living human hair, assumes high sheen, good feel (hand or grip) and very high elasticity even with the use of very hard water, in contrast to the conventional agents whose action and eifect are severely diminished by hard water.

The invention now will be further explained by the following examples. However, it should be understood that these are given merely by way of illustration, and not of limitation, and that numerous changes may be made in the details without departing from the spirit and thescope of the invention as hereinafter claimed.

Unless otherwise specified, all parts and percentages are by weight; the temperatures are in degrees Centigrade. Solutions are aqueous. The hardness degrees are so-called d.H., i.e., degrees of German hardness, a German industrial standard, wherein 1 d.H. equals 10 mg. CaO per liter.

EXAMPLE 1 As a solution for rendering hair blond, a 6% H O solution was used whose pH was adjusted to 10 with ammonia, shortly before application. These solutions were produced with water of different hardness degrees. To the hard water, 0.1% of an acylation product of phosphorous acid were added having Formula 7 I HOH OH and 6% H and the solution adjusted with ammonia to a pH of (solution 1). In other solutions, the compoundof Formula 7 was replaced by equal quantities of aminotri-(methylenephosphonic acid) (solution 2), and of a mixture of equal parts of the compound of Formula 7 and aminotri-(methylenephosphonic acid) (solution 3).

When the hardness of the water employed was more than 30, solution 1 was cloudy while solutions 2 and 3 remained clear even at a hardness up to 50.

Living human hair treated with solutions 2 and 3 developed a high gloss and sheen, even with the use of water of up to 50 hardness. Treatment was carried out 'at customary washing temperatures, i.e., ranging from room temperature to approximately 40 C.

The hair treated with solutions 2 and 3 exhibited practically the same alkali solubility as those treated with solution 1. The alkali solubility was considerably lower and, hence, the damage incurred by the hair, than in instances wherein the same blonding agent had been applied, but without the employment of the agents according to the invention.

The softening coefficient (K -value) which increases with increasing damage to the hair was more than 33% below the value when the same blonding agent without the additives according to the invention were used. Bleaching or blonding was carried out in each instance for 120 minutes. The K -value was determined according to the method of J. Mimra (Parfuemerie and Kosmetic, 42, No. 7, 61, pp. 253-260).

EXAMPLE 2 '8 parts fatty alcohol, 7 parts of a fatty alcohol sulfate (chain length for both C -C and one part fatty alcohol (C C were melted together by heating to 80 and emulsified with 34 parts water of the same temperature. The cream thus obtained was allowed to cool to room temperature and adjusted to a pH of 10.0 with 4 parts concentrated ammonia. This then was made up to 100 parts with water. For the bleaching of human hair, 100 g. of the cream were stirred with 30 g. of a mixture of 28 g. melamine perhydrate and 2 g. ethylenediaminotetra- (methylenephosphonic acid) in the form of its sodium salt. This mixture was evenly distributed over the hair and allowed to act for the customary period of time. Even by using water of more than 30 hardness, the hair thus treated had especially high gloss and more than average physical and mechanical properties.

EXAMPLE 3 A bleaching or blonding agent in paste form was produced by dissolving 30 parts of the addition product of stearyl alcohol with 8 mols ethylene oxide, 20 parts parafiin oil, 10 parts glycerol, 4 parts concentrated ammonia, in 36 parts Water. The highly viscous paste then was mixed with 5 g. sodium perborate and 0.2 g. of a mixture of equal parts aminoethane-l,l-diphosphonic acid monoethylester and aminotri-(methylenephosphonic acid). Hair bleached with this agent had good hand or grip, high gloss and good elasticity, even when very hard water was used.

EXAMPLE 4 A bleaching agent for human hair was prepared as a powder by mixing 25 parts alkyl sulfate, 50 parts soda, 20 parts sodium persulfate and 5 parts of a mixture of equal parts hydroxyethane-l,l-diphosphonic acid and ethylenediaminotetra-(methylenephosphonic acid) in the form of their potassium salts.

Damage to the hair treated with this product was considerably decreased over that incurred with the same bleaching agent devoid of the additives according to the invention. Albeit water of more than 30 hardness was used, the hair had high gloss.

EXAMPLE 5 100 parts of a dyeing cream based on conventional oxidation dyes were stirred together, just prior to application, with 0.2 part of a mixture of 20% hydroxyethane- 1,1-diphosphonic acid and aminotri-(isopropylenephosphonic acid) in the form of their ammonium salts, and 30 parts 6% H 0 Living human hair, dyed with this agent, exhibited particularly beautiful sheen and good hand or feel. The rate of damage was less than when the additives according to the invention had been omitted.

EXAMPLE 6 A liquid bleach was obtained by dissolving 1 part ethylene-diaminotetra (methylenephosphonic acid) in form of its monoethanolamine salt in 80 parts 10% H 0 The pH was adjusted to 10 by addition of monoethanolamine, and the solution made up to with Water. Damage to hair treated therewith was considerably less than with a comparative bleach which did not contain the products according to the invention.

EXAMPLE 7 Living human hair was rinsed, prior to bleaching, with a solution containing 10 parts aminotri (methylenephosphonic acid) in the form of its ammonium salt and 10 parts cetyltrimethylammonium chloride per 100 parts water. Bleaching or blonding then was carried out With an H 0 solution in the customary manner. The hair thus pretreated had better elasticity than hair not rinsed with the agent described. Even when using very hard water, high gloss and good hand or feel were obtained.

We claim as our invention:

1. A composition for the prevention of damage to hair upon dyeing and bleaching and for the improvement of gloss, elasticity and grip of said hair in the presence of very hard water which comprises a bleach, a carrier and 0.01 to 10 percent of a mixture of an aminopolyphosphonic derivative selected from the group consisting of aminopolyphosphonic acid, their water-soluble methanol, ethanol, butanol and amyl alcohol esters, and their sodium, potassium, ammonium, and ethanolamine salts, said aminopolyphosphonic acid having the formula wherein X and Y are selected from the group consisting of hydrogen and alkyl having 1 to 4 carbon atoms; and R and R are selected from the group consisting of PO H and a group having the formula and a polyphosphonic derivative selected from the group consisting of phosphonic acids, their Water-soluble methanol, ethanol, butanol, and amyl alcohol esters, and their sodium, potassium, ammonium, and ethanolamine salts; said phosphonic acid having the formula wherein R and R are selected from the group consisting of hydrogen and alkyl having 1 to 5 carbon atoms; X is selected from the group consisting of OH and NH and R is selected from the group consisting of phenyl, methyl and a group having the formula said aminopolyphosphonic derivative and said polyphosphonic derivative being in a weight ratio of 3:1 to 1:3.

2. The composition as defined in claim 1, wherein said aminopolyphosphonic acid is selected from the group consisting of aminotri (l-ethylphosphonic acid), ethylenediaminotetra (1 ethylphosphonic acid), aminotri-(lpropylphosphonic acid), aminotri (isopropylphosphonic acid) aminotri (methylenephosphonic acid), ethylenediaminotetra (methylenephosphonic acid), and diethylenetriaminopenta (methylphosphonic acid), and mixtures thereof.

3. The composition as defined in claim 2, wherein said aminopolyphosphonic acid is aminotri (methylenephosphonic acid).

4. The process for the prevention of damage to hair upon bleaching or dyeing With oxidizing dyes and for the improvement of gloss, elasticity and grip of said hair in the presence of hard water which consists essentially of treating said hair either prior to or together with the a plication to the hair of a bleach, with a composition of an aqueous carrier containing from 0.01 to percent by weight of a phosphonic acid composition selected from the group consisting of (l) aminoployphosphonic derivatives selected from the group consisting of aminophosphonic acids, their water-soluble methanol, ethanol, butanol and amyl alcohol esters, and their sodium, potassium, am-

monium, and ethanolamine salts, said aminopolyphos phonic acid having the formula wherein X and Y are selected from the group consisting of hydrogen and alkyl having 1 to 4 carbon atoms, and R and R are selected from the group consisting of -PO H and X (k-POgl-Tg and (2) mixtures of said aminopolyphosphonic derivatives and a polyphosphonic derivative selected from the group consisting of phosphonic acids, their Water-soluble methanol, ethanol, butanol, and amyl alcohol esters, and their sodium, potassium, ammonium, and ethanolamine salts; said phosphonic acid having the formula wherein R and R are selected from the group consisting of hydrogen and alkyl having 1 to 5 carbon atoms; X is selected from the group consisting of OH and NH and R is selected from the group consisting of phenyl, methyl and a group having the formula 0R 01|o11 OH2CX 0=1l 0H 0R2 References Cited UNITED STATES PATENTS 3,234,140 2/1966 Irani 260502.5 X 3,288,846 11/1966 Irani et al. 260-5025 3,394,172 7/1968 Schiefer 260502.5

ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner US. Cl. X.R.. 

